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WO2018057367A1 - Élimination de contaminants du pétrole brut - Google Patents

Élimination de contaminants du pétrole brut Download PDF

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Publication number
WO2018057367A1
WO2018057367A1 PCT/US2017/051340 US2017051340W WO2018057367A1 WO 2018057367 A1 WO2018057367 A1 WO 2018057367A1 US 2017051340 W US2017051340 W US 2017051340W WO 2018057367 A1 WO2018057367 A1 WO 2018057367A1
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WO
WIPO (PCT)
Prior art keywords
aqueous phase
partitioning
acid
interest
levels
Prior art date
Application number
PCT/US2017/051340
Other languages
English (en)
Inventor
Chengxiang Zhou
Ming Wei
Jason ENGLISH
Craig Hackett
Original Assignee
Bp Corporation North America Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bp Corporation North America Inc. filed Critical Bp Corporation North America Inc.
Priority to EP17784434.7A priority Critical patent/EP3516013A1/fr
Priority to RU2019110587A priority patent/RU2761458C2/ru
Priority to CA3035779A priority patent/CA3035779A1/fr
Priority to CN201780057847.5A priority patent/CN109790472B/zh
Publication of WO2018057367A1 publication Critical patent/WO2018057367A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/02—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
    • C10G17/04—Liquid-liquid treatment forming two immiscible phases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/02—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
    • C10G17/04—Liquid-liquid treatment forming two immiscible phases
    • C10G17/06—Liquid-liquid treatment forming two immiscible phases using acids derived from sulfur or acid sludge thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2823—Raw oil, drilling fluid or polyphasic mixtures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2835—Specific substances contained in the oils or fuels
    • G01N33/2876—Total acid number
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Definitions

  • the present invention relates to a method for correlating partitioning levels of a basic contaminant and/or an acid of interest from a hydrocarbon fluid with pH.
  • the correlations may be used in a method for selecting an acidic environment for use in a partitioning process in which a basic contaminant is partitioned from a hydrocarbon fluid into an aqueous phase.
  • the present invention is of particular use in crude oil desalting operations, since it enables basic contaminants, such as ammonia, organic amines and metal salts, to be removed during a desalting operation without unnecessary over-acidification of the crude oil.
  • Crude oil contains a number of contaminants which are desirably removed before the crude oil is processed.
  • Amines are a common unwanted contaminant.
  • Nitrogen-containing compounds which are used for this purpose include triazines, in particular monomethylamine triazine (MMA-triazine) and monoethanol amine triazine (MEA- triazine) which react with hydrogen sulfide to given dithiazine compounds and the free amines, i.e. MMA and MEA, respectively.
  • MMA-triazine monomethylamine triazine
  • MEA- triazine monoethanol amine triazine
  • aqueous phase contains water (that which was present in the extracted crude oil, as well as water that has been added to the hydrocarbon stream during processing, such as wash water) and contaminants.
  • a rag layer separates the two phases.
  • the rag layer is a mixture of the aqueous phase and the desalted crude oil phase.
  • a desalted crude oil stream and an aqueous stream are withdrawn from the desalter through separate lines.
  • the streams are typically withdrawn at points in the desalter which are a distance from the rag layer so as to minimise the presence of any aqueous
  • WO 2004/020553 discloses acidic compositions for removing metals and/or amines, whilst minimising oil carryunder, in a refinery desalting process.
  • Preferred compositions comprise, in addition to aeidifiers, corrosion inhibitors, demulsifiers, pH adjusters, metal chelants, scale inhibitors and hydrocarbon solvents. Accordingly, it can be seen that the compositions disclosed in WO 2004/020553 are designed as finely tuned additive packages for use in commercial desalting processes.
  • Water-soluble hydroxyacids are used as an acidifier in WO 2004/020553 in place of commodity acids such as acetic acid, since these hydroxyacids are believed to exhibit lower levels of partitioning into the oil during the refinery desalting process.
  • the use of specific water-soluble hydroxyacids in a commercial desalting operation can turn out to be expensive and restricting, e.g. as compared to methods in which commodity acids may be used.
  • compositions disclosed in WO 2004/020553 also comprise a mineral acid in an amount sufficient to reduce the pH of the wash water to 6 or below. Whilst a lower pH is generally believed to favour movement of metals and/or amines into the aqueous phase, it has now been found that the elevated temperature and/or pressure that is typically used in a commercial desalter may have a significant effect on pH and thus the partitioning of both contaminants and acids between the aqueous and non-aqueous phases. Accordingly, the use of correlations between ambient pH and partitioning in selecting conditions for a commercial desalting process may be of limited benefit.
  • the present invention is based on the discovery that the proportion of basic contaminant (e.g. ammonia, organic amine or metal salt contaminant) that is partitioned into the aqueous phase is strongly dependent on the pH of the aqueous phase at process conditions, which may differ significantly from the pH of the aqueous phase measured under ambient conditions.
  • the partitioning of an acid has also been found to be strongly dependent on the pH of the aqueous phase at process conditions.
  • the correlations between partitioning levels and process pH are largely independent of the nature of the acid or base that is used to control the pH, with lower pH favouring successful contaminant partitioning into the aqueous phase, and higher pH favouring successful partitioning of the acids into the aqueous phase.
  • the present invention provides a method comprising:
  • the present invention further provides a method for selecting an acidic environment for use in a partitioning process in which a basic contaminant is removed from a hydrocarbon fluid, said method comprising:
  • a method for estimating corrosion risk downstream of a partitioning process in which a basic contaminant is removed from a hydrocarbon fluid comprising estimating the corrosion risk based on correlations determined using the methods disclosed herein.
  • the present invention also provides a database comprising:
  • partitioning levels of the basic contaminant and the acid of interest, as well as the pH of the aqueous phase have been obtained under conditions which are representative of those used in a partitioning process in which a basic contaminant is removed from a hydrocarbon fluid.
  • the database may be used in a method for selecting an acidic environment for a partitioning process in which a basic contaminant is removed from a hydrocarbon fluid, for estimating corrosion risk downstream of a partitioning process in which a basic
  • Figs. la ⁇ c are graphs depicting the correlation between partitioning levels of different amines with aqueous phase pH measured under process conditions
  • Figs. 2a-g are graphs depicting the correlation between partitioning levels of different acids with aqueous phase pH measured under process conditions
  • Figs. 3a-f are graphs depicting the correlation between partitioning levels of
  • Figs. 4a ⁇ b are graphs depicting the effect of temperature on the pH of aqueous phases acidified using different acids.
  • Figs. 5a ⁇ b are graphs depicting the correlation between partitioning levels of
  • the present invention provides a method for correlating - in a system which comprises a non-aqueous phase comprising a hydrocarbon fluid, and an aqueous phase - partitioning levels of a basic contaminant and/or an acid of interest with the pH of the aqueous phase.
  • correlations are obtained for both a basic contaminant and an acid of interest.
  • species other than the basic contaminant and the acid of interest may be present in the systems, including further acids, bases and salts (e.g. those species that may typically be present in crude oil streams in a refinery).
  • the basic contaminant may be selected from ammonia, organic amines, salts, and combinations thereof. These contaminants are typically found in hydrocarbon fluids such as crude oil or other refiner ' feedstocks. Optimising the removal of such contaminants is highly desirable in industrial partitioning processes, such as a desalting process in a refinery.
  • Organic amine contaminants may be selected from monomethylamine, ammonia, and monoethanol amine, diethanolamine, ethylamine, diglycolamine, methyidieihanoiamiiie, dimethylethanolamine, trimethylamine, propylamine, morpholine,
  • amine contaminants are often found in hydrocarbons fluids such as crude oil and are implicated in problems with corrosion and fouling downstream in a refinery. However it will be appreciated that these amine contaminants are merely exemplar ⁇ ' and a wide range of amine contaminants may be found in the hydrocarbon fluid.
  • Salt contaminants may be selected from metal salts and combinations thereof, with the metal typically being a group 1 or group 2 metal.
  • the contaminant is selected from sodium salts, potassium salts, calcium salts, iron salts and combinations thereof. These salt contaminants, e.g. in their chloride form, are often found in
  • hydrocarbons fluids such as crude oil .
  • the basic contaminant is selected from monomethylamine,
  • the method of the present invention may be used for selecting an acidic environment for use in a partitioning process in which ammonia, at least one organic amine and at least one basic salt are removed from crude oil.
  • the system may comprise the basic contaminant in an amount of from 0.1 to 300, preferably from 0.5 to 100, and more preferably from 1 to 50 ppm by weight.
  • the acid of interest may be a single acid or a mixture of acids.
  • the method of the present invention comprises repeating step (b) for a plurality of acids of interest. This enables correlations for a number of acids of interest to be prepared.
  • the method of the present invention may comprise repeating step (b) for at least 3 acids of interest, preferably at least 4 acids of interest, and more preferably at least 6 acids of interest.
  • the acid of interest is selected from hydrochloric acid, acetic acid, glycolic acid, citric acid, malic acid, maleic acid, hydrogen sulfide, carbon dioxide, and mixtures thereof.
  • Other acids such as other carboxylic acids, may also be used.
  • Hydrogen sulfide and carbon dioxide are acidic in the aqueous phase of the system.
  • Hydrogen sulfide and carbon dioxide are contaminants that are commonly found in crude oil. They are generally not desired in the system and so, whilst they may be present, they will generally not be added as an acidifying agent to the system.
  • the hydrocarbon fluid is preferably a refiner ⁇ ' feedstock, such as a crude oil.
  • Crude oils contain the basic contaminants discussed herein, such as ammonia, organic amines and salts. Accordingly, when a crude oil is used, the basic contaminants may be introduced into the sy stem via the crude oil.
  • the partitioning process is preferably a desalting process, e. . in a refinery.
  • Steps (a) and (b) of the method of the present invention involve correlating partitioning levels of a basic contaminant and an acid of interest, respectively, into the aqueous phase with the pH of the aqueous phase.
  • the method may comprise obtaining the partitioning levels of the basic contaminant into the aqueous phase at a plurality of pH levels under conditions which are representative of those used in the partitioning process.
  • the method may also comprise obtaining the partitioning levels of the acid of interest into the aqueous phase at a plurality of pH levels under conditions which are representative of those used in the partitioning process.
  • the method comprises obtaining the partitioning levels of the basic contaminant and the acid of interest into the aqueous phase at a plurality of pH levels under conditions which are representative of those used in the partitioning process. It will be appreciated that the results that are obtained will be used for the correlations in steps (a) and (b) of the method.
  • the method may further comprise providing the system which comprises the contaminant, a non-aqueous phase comprising a hydrocarbon fluid, and an aqueous phase (i.e. the system referred to in step (a) of the method), e.g. by contacting a hydrocarbon fluid comprising the contaminant with water.
  • the method may also comprise providing the system which comprises an acid of interest, a non-aqueous phase comprising a hydrocarbon fluid, and an aqueous phase (i.e. the system referred to in step (b) of the method), e.g. by contacting a hydrocarbon fluid with an aqueous acid solution.
  • the systems referred to in steps (a) and (b) of the method will each generally comprise water in an amount of from 0.5 to 20 %, preferably from 1 to 15 %, and more preferably from 3 to 10 % by weight of the system.
  • the systems are preferably subjected to mixing before the partitioning levels of the acid of interest and the contaminant are obtained. This facilitates partitioning of contaminants that are originally present in the non-aqueous phase (e.g. as part of a caide oil) into the aqueous phase. Methods for mixing are known in the art.
  • the partitioning levels of each of the basic contaminant and the acid of interest into the aqueous phase may be calculated as follows:
  • Partitioning level (by weight)
  • the amount of contaminant and acid of interest may be obtained by direct measurement, modelling, or combinations thereof.
  • Ion chromatography IC
  • IC ion chromatography
  • Known electrolyte modelling techniques may also be used.
  • the partitioning levels of the acid of interest and the contaminant may be obtained at a plurality of pH levels between 1 and 10, preferably between 2 and 8, and more preferably between 3 and 7.
  • the partitioning levels may be measured at a pH of less than 4, at a pH of greater than 6 and at one or more pH levels therebetween .
  • These pH levels are generally preferred for partitioning processes for practical reasons (e.g. corrosion control); it will be appreciated that the preferred pH levels for partitioning will vary based on the chemical nature of the particular basic contaminant and acid of interest used.
  • the partitioning levels are preferably obtained at greater than 4, more preferably greater than 6, and still more preferably greater than 10 pH levels.
  • the pH of the aqueous phase is varied by modifying the amount of acid that i s present in the systems referred to in steps (a) and (b).
  • the amount of acid in the systems is preferably varied by adding varying amounts of the acid of interest, but may also be varied by adding varying amounts of one or more further acids.
  • the pH of the aqueous phase may be measured directly or indirectly.
  • Direct determination of the pH of the aqueous phase involves direct measurement of pH of the aqueous phase under conditions which are representative of those used in the partitioning process, e.g. elevated temperature and pressure. Suitable pH meters for carrying out such measurements are known in the art.
  • the pH of the aqueous phase is determined indirectly.
  • the pH may be estimated using a method which comprises: analysing the aqueous stream to determine the content of different organic and inorganic components (e.g. amines, acids and salts) and, based on the analysis, estimating the pH under different conditions using known electrolyte modelling tools. Other established tools may also be used for estimating the pH.
  • a crucial aspect of the present invention is that the partitioning levels of the contaminant and the acid of interest, as well as the pH of the aqueous phase, have been obtained (or are measured, in embodiments where this forms part of the method of the present invention) under conditions which are representative of those used in the partitioning process. This is important because the pH of the systems disclosed herein may var greatly when measured under ambient conditions as compared to process conditions.
  • the partitioning levels and pH are obtained at a temperature which is representative of (e.g. the same as) that used in the partitioning process, such as a temperature in the range of from 20 to 300 °C, preferably from 80 to 150 °C, and more preferably from 1 10 to 140 °C.
  • the partitioning levels and pH are obtained at a pressure which is representative of (e.g. the same as) that used in the partitioning process, such as a pressure in the range of from 100 to 3000 kPa, preferably from 500 to 2500 kPa, and more preferably from 1000 to 2000 kPa.
  • a high temperature is preferably accompanied by the use of a high pressure, as is the case in industrial desalting operations, so that the more volati le components in the systems are substantially maintained in the liquid phase.
  • the correlation between partitioning level and pH may be expressed using the following formula:
  • partitioning level (%) ;: ax 6 +bx 3 +cx 4 +dx 3 +ex 2 +fx+g where: x is the pH of the aqueous phase under process conditions; and
  • a to g are constants.
  • the constants a to g will vary for each basic contaminant and acid of interest.
  • the constants may be determined using known polynomial methods. Selecting an acidic environment
  • the correlations determined in steps (a) or (b), and preferably steps (a) and (b), of the method disclosed herein are used for selecting an acidic environment for use in a partitioning process in which the basic contaminant is removed from a hydrocarbon fluid.
  • the step of selecting an acidic environment comprises selecting a pH for the aqueous phase that is present in the partitioning process.
  • the step of selecting an acidic environment preferably also comprises selecting an acid from the plurality of acids of interest for use in the partitioning process.
  • the acidic environment is preferably selected because it correlates with a target level of basic contaminant partitioning into the aqueous phase, for instance a target partitioning level of greater than 50 %, preferably greater than 70 3 ⁇ 4, and more preferably greater than 90 %.
  • the selected acidic environment also correlates with a target level of acid of interest partitioning into the aqueous phase, for instance a target partitioning level of greater than 50 %, preferably greater than70 %, and more preferably greater than 90 %. Though these ranges are preferred, it will be appreciated that the target levels of partitioning for some contaminants and acids of interest may be less than 50 %.
  • the step of selecting the acidic environment may comprise: in a first step, limiting the possible acidic environments to those which can provide a target contaminant partitioning level and, in a second step, further limiting the possible acidic environments to those which can provide a target acid of interest partitioning level.
  • the acidic environment may then be selected from the subset of possible acidic environments, e.g. based on economic factors. For instance, where a plurality of acids of interests have been considered, the minimum amount of each acid that would be required to achieve a pH which correlates with a target contaminant partitioning level and a target acid of interest partitioning level may be calculated. The monetary cost of running the partitioning process with each acid of interest could then be calculated, and the cheapest option selected.
  • an acidic environment may be used in a partitioning process in which the basic contaminant is removed from a hydrocarbon fluid.
  • a method for controlling a partitioning process comprises: (i) selecting an acidic environment using the methods disclosed herein; and (ii) operating the partitioning process with the acidic environment selected in (i).
  • the correlation between the partitioning levels and pH will be highly variable for different basic contaminants. Accordingly, it will be understood that the contaminant that is used in the method for selecting the acidic environment is the same as the contaminant which is removed from the hydrocarbon fluid in the method for optimising a partitioning process.
  • hydrocarbon fluid that is used in the method of selecting the acidic environment does not necessarily have to be the same as that which used in the method for optimising a partitioning process.
  • the use of the same hydrocarbon fluid is highly preferred, since the properties of the hydrocarbon fluid (e.g. origin, API gravity , distillation profile, etc.) can have an effect on the correlation between partitioning levels of the contaminant and acid of interest with the pH of the aqueous phase.
  • Preferred hydrocarbon fluids are those mentioned previously in connection with the method of selecting the acidic environment, with crude oil highly preferred.
  • the partitioning process is operated at a temperature in the range of from 20 to 300 °C, preferably from 80 to 1 50 °C, and more preferably from 110 to 140 °C,
  • the partitioning process is operated at a pressure in the range of from 100 to 3000 kPa, preferably from 500 to 2500 kPa, and more preferably from 1000 to 2000 kPa.
  • the partitioning process may be a desalting process that is carried out in a desalting unit, e.g. in a refinery. Crude oil is preferably used as the feedstock for the desalting operation.
  • a desalting unit will typically have an inlet, a hydrocarbon outlet and an aqueous outlet.
  • the crude oil (containing the contaminant), and wash-water are introduced into the desalter via the inlet.
  • the crude oil and wash-water are mixed, e.g. by being passed through a mixing valve, to encourage partitioning of the contaminant from the crude oil to the aqueous phase.
  • a non-aqueous phase comprising crude oil is removed from the desalter via the hydrocarbon outlet.
  • An aqueous phase is removed from the desalter via the aqueous outlet.
  • Wash-water may be added to the crude oil in an amount of from 0.5 to 20 %, preferably from 1 to 15 %, and more preferably from 3 to 10 % by total weight of crude oil and wash-water.
  • the selected acidic environment may be achieved in the partitioning process by introducing appropriate quantities of acid into the partitioning process, e.g. by acidification of the wash water.
  • Other methods for achieving an aqueous phase having a selected pH include introducing into the partitioning process appropriate quantities of one or more of the following components: bases, H 2 S scavengers, calcium removal agents and neutralises.
  • the method for controlling the partitioning process comprises, in step (i), selecting a pH for the aqueous phase that is present in the partitioning process.
  • the method preferably further comprises monitoring the pH of the aqueous phase in the partitioning process at process conditions, and maintaining the pH of the aqueous phase at the selected pH.
  • the pH of the aqueous phase may be monitored using those methods described above, i.e. by direct or indirect measurement.
  • the pH of the aqueous phase is monitored by indirect measurement, e.g. using those methods outlined above.
  • the pH of the aqueous phase in a desaiter is either monitored at ambient conditions, which may differ significantly from the pH under process conditions, or is not monitored at all.
  • the conditions ⁇ e.g. temperature and pressure) in the partitioning process are also monitored.
  • the compositions of the components in the aqueous phase may also be analysed. This allows variations in the conditions in the partitioning process to be reflected in the indirect measurement of pH.
  • the pH of the aqueous phase may be maintained by modifying the amount of acid of interest, or other acid, that is introduced into the partitioning process.
  • the pH may be maintained by varying the degree to which the wash-water is acidified.
  • Other methods include modifying the amount in which of one or more of the following components are introduced into the partitioning process: bases, H 2 S scavengers, calcium removal agents and neutralisers.
  • the pH of the aqueous phase is maintained by modifying the amount of acid and base that is introduced into the partitioning process.
  • the pH may be maintained within ⁇ 0.5 pH units, preferably within ⁇ 0.3 pH units, and more preferably within ⁇ 0.1 pH units of the pH that was selected for the aqueous phase in step (i). This means that, where a pH of 4.0 has been selected for the acidic environment, the aqueous phase is maintained at a pH of from 3 ,5 to 4.5, preferably from 3.7 to 4.3, and more preferably from 3.9 to 4.1.
  • a closed-loop control system may be used for monitoring and maintaining the pH of the aqueous phase, e.g. where an online pH meter is used with the partitioning process.
  • the method for controlling the partitioning process may be used to optimise the partitioning process.
  • the method optimises the partitioning process by increasing the proportion of contaminant that is removed from the hydrocarbon fluid.
  • the method also optimises the partitioning process by reducing the proportion of acid of interest that is present in the non-aqueous stream.
  • An optimised partitioning process preferably increases the partitioning level of contaminant into the aqueous phase to greater than 50 %, preferably greater than 70 %, and more preferably greater than 90 %.
  • An optimised partitioning process preferably also achieves a partitioning level of acid of interest into the aqueous phase of greater than 50 %, preferably greater than 70 %, and more preferably greater than 90 %,
  • the method for controlling the partitioning process may also be used optimise refinery processes that are found downstream of the partitioning process and which benefit from an improvement in the partitioning process.
  • the processes described herein may be to reduce corrosion and fouling downstream of the partitioning process.
  • the correlations obtained using the methods of the present invention may also be used for estimating corrosion risk downstream of the partitioning processes disclosed herein.
  • the present invention also provides a database which comprises: a correlation - in a system which comprises a basic contaminant, a non-aqueous phase comprising a hydrocarbon fluid, and an aqueous phase - between the partitioning level of the
  • the database comprises correlations for at least 2, preferably at least 4, and more preferably at least 8 basic contaminants.
  • the database may alternatively comprises a correlation - in a system which comprises an acid of interest, a non-aqueous phase comprising a hydrocarbon fluid, and an aqueous phase - between the partitioning level of the acid of interest into the aqueous phase with the pH of the aqueous phase.
  • the database preferably comprises correlations for at least 2, preferably at least 4, and more preferably at least 8 acids of interest.
  • the database comprises at least one correlation between the partitioning level of the basic contaminant into the aqueous phase with the pH of the aqueous phase, and at least one correlation between the partitioning level of the acid of interest into the aqueous phase with the pH of the aqueous phase.
  • the database may be stored on a computer readable medium, or it may be stored as a cloud database.
  • the database may be used in carrying out the methods of selecting an acidic environment disclosed herein, so that the partitioning levels of the contaminant and the acid of interest into the aqueous phase at a plurality of process pH levels do not have to be measured and the correlations in steps (a) and (b) can be obtained directly from the database.
  • the database may be used in a method of selecting an acidic environment for a partitioning process in which a contaminant is removed from a hydrocarbon fluid, the contaminant being an amine or a salt.
  • the database may also be used in methods disclosed herein for estimating corrosion risk downstream of a partitioning process in which a basic contaminant is removed from a hydrocarbon fluid, or for controlling (e.g. optimising) a partitioning process in which a basic contaminant is removed from a hydrocarbon fluid.
  • Example 1 Correlating partitioning levels of amine contaminants with process pH
  • Partitioning levels for the amines monomethylamine (MMA), monoethanolamine (MEA) and ammonia (N3 ⁇ 4) were measured across a range of pH levels at process conditions. A number of different acids were used to control the pH in the experiments. Further additives were also introduced into the system (such as further bases and metal salts) to investigate whether the presence of different types of additive may have an effect on the coiTelation between amine partitioning levels and process pH. Graphs depicting the correlations are shown in Figs. la-c.
  • Example 2 Correlating partitioning levels of acids of interest with process pH
  • Partitioning levels for the acids acetic acid (AcOH), hydrochloric acid (HQ), citric acid, giycolic acid, malic acid, maleic acid, and H 2 S were measured across a range of pH levels. A number of different bases were used to control the pH in the experiments.
  • Example 3 Selecting acidic conditions for use in a partitioning process Correlations between the partitioning levels and the pH of the aqueous phase for monoethanolamine were plotted against correlations between the partitioning levels and the pH of the aqueous phase for six different acids of interest: acetic acid, glycolic acid, maleic acid, malic acid, citric acid and hydrochloric acid. Graphs depicting the
  • Each of the other acids exhibited a high l evel of partitioning into the aqueous phase (approximately 99 %) at a pH of 5.
  • hydrochloric acid was not selected for use in the partitioning process due to its relatively corrosive nature. Accordingly, an acidic environment was selected in which at least one of maleic acid, malic acid and citric acid were used.
  • Example 4 Effect of temperature on the pH of an aqueous phase
  • Monomethylamine and monoethanolamine were acidified to an ambient conditions pH of 5.5 and 6, respectively, using a variety of different acids. Change in pH with temperature was then measured. The results are shown in Figs. 4a-b.
  • Example 5 Correlating partitioning levels of an amine contaminant with pH as measured under ambient conditions and process conditions Partitioning levels for monoethanolamine with a number of different acids were measured under process conditions and correlated against the pH of the aqueous phase measured under ambient conditions. A graph of the results is shown in Fig. 5a.
  • monoethanolamine partitioning level and ambient pH any correlation varies greatly based on the acid that is used in the system. For example, at an ambient pH of 6.0, the amount of monoethanolamine that is still present in the oil can vary from 2.5 % (when hydrochloric acid is used in the system) to 12,5 % (when maleic acid is used).
  • Fig. 5b shows the strong correlation that is observed between partitioning level of monoetha olamine and process pH, irrespective of the acid that is used in the system.
  • the partitioning level (%) into the aqueous phase has been expressed in terms of the formula ax 0 +bx 5 +cx 4 +dx J +ex 2 +fx+g, where x is the pH of the aqueous phase.

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Abstract

Un procédé consiste à mettre en corrélation - dans un système qui comporte une phase non aqueuse comprenant un fluide hydrocarboné, et une phase aqueuse - des niveaux de séparation d'un contaminant basique et/ou d'un acide d'intérêt dans la phase aqueuse avec le pH de la phase aqueuse. Les niveaux de séparation du contaminant basique et de l'acide d'intérêt, ainsi que le pH de la phase aqueuse, sont obtenus dans des conditions qui sont représentatives de celles utilisées dans un processus de séparation dans lequel un contaminant basique est éliminé d'un fluide hydrocarboné. Les corrélations peuvent être utilisées dans un procédé de sélection d'un environnement acide pour une utilisation dans un processus de séparation, d'estimation d'un risque de corrosion en aval d'un processus de séparation, ou de commande d'un processus de séparation.
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WO2004020553A1 (fr) 2002-08-30 2004-03-11 Baker Hughes Incorporated Additifs permettant d'accroitre l'elimination de metaux et amines dans des processus de raffinage-dessalement
WO2007005298A2 (fr) * 2005-06-30 2007-01-11 Cpc Corporation, Taiwan Procede de production d'huiles de petrole a tres faible teneur en azote
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US11965131B2 (en) 2018-12-21 2024-04-23 Equinor Energy As Treatment of produced hydrocarbons

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RU2019110587A3 (fr) 2020-12-17
US20180079969A1 (en) 2018-03-22
CN109790472B (zh) 2021-06-01
US10883054B2 (en) 2021-01-05
CA3035779A1 (fr) 2018-03-29

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